Lecture Notes

On
Corrosion Engineering

Course code: Th4

Semester: 6th
Course Co-ordinator: Goutam Kumar Majhi (Lect.)
Metallurgical Engineering Department
Utkalmani Gopabandhu Institute of Engineering
Rourkela-769004
Session: 2021-22
 INTRODUCTION TO CORROSION

Definition
 It is the loss of material as a result of chemical or
electrochemical reaction with its environment.

 This phenomena is most likely occur in metals as compare

to ceramics or plastics.
Ex- Rusting of steel, tarnishing of silver.

 Corrosion engineering is the science & art to protect

materials from corrosion economically & safely.

Cost of corrosion

 Losses due to corrosion could be direct or indirect.

Direct loss

1. Inability to use desired materials.

2. Over-design/ allowance for corrosion component.
3. Cost of repair or replace of corroded component.
4. The cost of anti-corrosive painting or other protection
methods.

Indirect loss
1. Contamination of product.
2. Loss of valuable product from a container that has
corroded through.
3. Loss of production.
4. Safety.
5. Loss of appearance.
Importance of corrosion studies

 Increasing use of metals in all fields of technology.

 Use of rare & expensive metal and alloys.
 Use of new high strength alloy which are prone to certain
type of corrosion.
 Increasing pollution of air & water which result in more
corrosive action.
 Strict safety standard.
Classification of corrosion

 Based on corrosion mechanism it is classified is to two

type:
1. Chemical corrosion.
2. Electro-chemical corrosion.

1. Chemical corrosion

 It involves direct chemical reaction of metal with its

environment.

2. Electro-chemical corrosion

 Here the environment act as a medium for corrosion.

Transfer of e-
Corrosion rate

 In corrosion engineering materials are compared on the

basis of their corrosion resistance.
  Most commonly corrosion rate are measured by the
weight loss due to corrosion.

The rate of corrosion can be calculated by:

R=KW / ATD (mpy or mm/yr)

Where, R = rate of corrosion
K = constant
W = weight loss in gm
A = area of specimen
T = time exposed
D = density in gm/cm3
 CORROSION PRINCIPLE
Electrochemical principle of corrosion:
 Corrosion of metal can take place either by chemical or
an electrochemical route or by both taking place
simultaneously.

Chemical Electrochemical
1. It takes place due to direct 1. It is due to formation of
chemical reaction of metal anodic area.
with the environment.
2. There is no transport of 2. Transport of charge through
charge. electrolyte.
3. Metal remains film free. 3. Formation of films
4. It occurs in dry condition. 4. Occurs in presence of
moisture or electrolyte.
5. Homogenous metal can get 5. Heterogeneous (bimetallic)
corroded. surface get corroded.
Chemical vs electrochemical corrosion

Types of reaction in corrosion

Oxidation
 Removal of electron (e-) from metal is called oxidation.

M  M+ + e-

Reduction

 Addition of electron is reduction.

M+ + e-  M(S)
  Summation of both the reaction is known as redox
reaction.

Electrolysis

 It is a process of passing electric current through an

electrolyte result in chemical reaction at the electrodes.

Faraday’s Law of electrolysis:

 Electrochemical process, including corrosion reactions

obey Faradays laws of electrolysis.

1st law

 When a current is passing through an electrolyte amount

of substance/material deposited or liberated at electrode is
directly proportional to the amount of electricity passed
through it.

WQ
(Q=i.t)
W= Z.i.t

Where, W= wt. of material deposited or liberated

i = Current passed
t = time
Z= Electro Chemical Equivalent

“Electro chemical equivalent (ECE) of a substance is defined

as the mass which is liberated or dissolved by the pass of a
current of 1amp for 1sec”.
2nd law

 “When same amount of electricity is passed through

different electrolyte, the mass of substance
deposited/liberated is directly proportional to their
chemical equivalent”.

WE
𝑊1 𝐸1
=
𝑤2 𝐸2
Where, W = wt. of material deposited/liberated.
E = chemical equivalent of the material.
(E = Atomic wt. / valency)

Deviation from Faraday’s law

 There is deviation for Faraday’s law is observed during

electrolysis due to following reasons :-

(a) Recombination of primary products

 There is chances of recombination of cathodic & anodic
products if the temperature rises.

(b) Discharge of other ions

 Loss of current occurs due to discharge of other ions
rather than the selected ion.

(c) Formation of compound

 It has been observed that in certain cases formation of
compound at electrodes.
(d) Dissolution of electrode
 Due to direct dissolution of electrode there will be error
in result.

(e) Evaporation losses

 In some cases due to high temperature evaporation of
metal occurs. Which will result in deviation in result.
 Type of electrochemical cell
Electrochemical Cell
 It is a device which either generate electrical energy from
chemical reaction or use electrical energy for chemical
reaction to occur.

Three main types of electrochemical cells are there which are

responsible for corrosion:

(i) Galvanic cell

(ii) Concentration cell
(iii) Electrolytic cell

(i) Galvanic cell

 It is a type of electrochemical cell which convert
chemical energy to electrical energy.
 This type of cell is generated whenever two dissimilar
metals are connected electrically.
 This dissimilarity could be due to:

(a) Two different metal

(b) Same metals undergone different heat
treatment processes
(c) Surface roughness
(d) Different grain size
(e) Chemical heterogeneity

 In this type of cell, the process consists of redox reaction.

That means one acts as anode where oxidation reaction
takes place and at the other reduction reaction takes place.
Redox= oxidation + reduction
 For example, if we connect Cu & Zn electrically then Zn
electrode will get oxidized (corrode).

Figure: Galvanic cell

(ii) Concentration cell

 In this type of cell, the material(s) may be homogenous in

all aspect so that there won’t be any cathodic or anodic
area but corrosion may occur due to difference in
electrolyte they are in contact with.

 It can be defined as the electro chemical cell which is a

result of difference in electrolyte.

 It also converts chemical energy to electrical energy or

chemical reaction results in movement of e- .
 Figure: Concentration cell

Difference in electrolyte could be due to:

(a) Different composition of electrolyte – electrodes are in
contact with two different electrolyte.
(b) Same electrolyte but different concentration- one is dilute
another is concentrated.
(c) Temperature difference- the two regions having different
temperature may have different potential.
(d) Different oxygen concentration.

(iii) Electrolytic cell

 It is a type of electrochemical cell which uses electrical

energy to drive a chemical reaction.

 When the metal(s) and electrolyte are homogenous to such

an extent that no cathodic and anodic area are developed,
in those cases presence of energy from external source can
develop cathodic and anodic area.
 Figure: Electrolytic cell
 Corrosion can occur in metal due to development of an
electrolytic cell for example, if current enters a metallic
structure at same point and leaves at another point, then
the area at which current leaves the metallic source
become anodic w.r.t to the other.

Difference between galvanic cell and electrolytic cell

Galvanic cell Electrolytic cell

(a) It converts chemical (a) It converts electrical
energy to electrical energy to chemical
energy. energy.

(b) Electrodes are of (b) Electrodes are of

dissimilar metals. similar metal.

(c) Here spontaneous (c) Here nonspontaneous

chemical reaction chemical reaction
takes place. takes place.
(d) No need of external (d) External power source
power source. is required.
(e) Anode is negative and (e) Cathode is negative
cathode is positive. and anode is positive.
 Chapter 4
Electrode Potential
 The potential difference between electrode and its ion in
the electrolyte is called as electrode potential.

 There is no practical method available to determine this

single electrode potential difference. Therefore,
measurements are always carried out between two metal-
solutions (electrode-electrolyte) for electrode potential
difference.
 For assigning value to single electrode potential, one of
the electrode potential is taken as reference potential and
assigned a value of zero potential.
EMF series

 Electromotive force series is an arrangement of metals

according to their electrode potential.
 For construction of emf series hydrogen is taken as
standard electrode (reference) and assigned an electrode
potential 0V.
 That means the series has been established by measuring
potential of various electrode versus standard H2
electrode.

Metals Electrode potential

Au………………………………….. +1.70
Pt……………………………………. +1.23
Cu………………………………….. +0.23
H2…………………………………….. 0
Ni………………………………………. -0.25
Fe …………………………………........ -0.44
Al………………………………………. -1.66

 Metal having higher (+ve) electrode potential remain

above hydrogen in the series and vice-versa.
 Higher the electrode potential of metal it is and less
tendency to oxidation and corrosion.
 Lower electrode potential metals are less stable, easily get
oxidized and corroded.
Application of EMF series

EMF series is very useful in predicting the type of reaction that

is taking place at an electrode.

1. Displacement of metals

 One metal will displace another metal which is present

above it in emf series.
 That means, higher electropositive metal will be reduced
and the less electropositive metal will get oxidised while
dipped in one of its aqueous solution.
 For example if a Zn rod is dipped in CuSo4 solution. Zn
will have higher tendency to remain in the solution than
Cu.
So Zn will lose electron to go into the solution, and those
electrons will be consumed by some Cu ion they get
reduced and deposited at Zn rod.

Zn2+

Cu

Figure: Displacement of Cu by Zn.

Zn  Zn2+ + 2e-
Cu2+ + 2e-  Cu(s)
2. Displacement of hydrogen

 Corrosion of many metals occurs via evolution of H2 gas,

i.e. H+ ion get reduced from the electrolyte and the
corresponding metal electrode get oxidised.

M  M+ + e-
2H+ + 2e-  H2 (g)

H2
M+

 Metals present above H2 in emf series, such as Gold, Pt,

Ag, Cu etc. are incapable of displacing/liberating H2 while
placed in acid. Whereas, metal present below H2 can
displace H2 from acid and get oxidised/corroded.

3. Galvanic Corrosion

 If two metals in the emf series are electrically connected

in an aqueous electrolyte, the series can be used to predict
which of them is likely to corrode.
 Looking from the potential value from the emf series the
more electronegative metal or the metal present lower in
emf series as compared to other will get corroded.
  The tendency of corrosion will increase if the metals are
placed widely apart in the series.

 For example if we connect Cu and Zn, then Zn will get

corroded.

Zn  Zn2+ + 2e-
Cu2+ + 2e-  Cu(s)
4. Electrolysis
 More electropositive metals (metals having higher
electrode potential) deposit first.
 For example, if a solution contains both H+ and Cu+ ions
then copper will liberate from the solution and deposit first
at cathode.
 This principle can be applied for separation of different
metals dissolved in solution.

Limitations of EMF series

1. Only pure metals are listed in the series. But in application

we rarely use pure metal. This series cannot predict
corrosion behaviour of alloys.
2. The electrode potential of metals listed in the series is
determined under specified condition, i.e. 1atm pressure
and 1molar electrolyte.
3. The emf series doesn’t take account of surface films,
which may form on the metal surface which shows
passivation.
Example: SS, Al etc.
4. Effect of temperature has not been considered in the emf
series. It is only applicable at a temperature of 25c.
 5. EMF series doesn’t take account the effect of pH value of
electrolyte.

Galvanic Series
 This series is an arrangement of metals and alloys w.r.t. to
their actual potential in a given environment.
 Galvanic series is a more practical chart showing relative
tendency to corrosion in a particular environment (such as
sea water)
 Magnesium at the end of the series is the most active, and
Pt is on the top of the list. (Table 13-6.2)
 Ti and Ni which are more active in the electrochemical
series are near the noble end of this galvanic series, by
virtue of their ability to form passive films.
 Galvanic series of some commercial metals and alloys in
sea water is given the table below:

Application and features of Galvanic series

 This series contains both metal and alloys.
 Metals and alloys present towards top of the series are
corroded least and those which are present at bottom
corroded maximum.
 The farther apart metal and alloys are in the series more
will be potential difference chances of corrosion will be
more. So farther apart metal/alloys shouldn’t be connected
electrically.
 Chances of corrosion is minimum when metals of same
group enclosed in brackets are connected together.
Limitations
 In case of emf series only one series exist but here can be
several numbers of Galvanic series depending upon the
environment of application.
 Corrosion between two metals connected electrically not
only depend on how far they are present in Galvanic series
but also the potential difference.
 This series also cannot be used to predict effect of change
in pH on corrosion tendency.
 CHAPTER 5

DIFFERENT FORMS OF CORROSION

Introduction:
 Corrosion manifest itself in various form.

 It is needed to know the type of corrosion that is taking

place in the given atmospheric condition.

 Because, valuable information for the solution of a

corrosion problem can often be obtained through careful
observation of the corroded test specimens or failed
equipment.

 The basis for this classification being the appearance of

the corroded metal. Each form can be identified by mere
visual observation. In most cases the naked eye is
sufficient, but sometimes magnification is helpful or
required.

Corrosion is classified into:

i. Atmospheric corrosion
ii. Intergranular corrosion
iii. Pitting corrosion
iv. Corrosion fatigue
v. Galvanic corrosion
vi. Stress corrosion cracking
vii. Cavitation corrosion
viii. Fretting corrosion
ix. High temperature oxidation corrosion
x. Stray current corrosion
i. Atmospheric corrosion

 Atmospheric corrosion is the attack of a metal or an alloy

by the atmospheric environment to which it is exposed.

 It represents the greatest destruction of metal on tonnage

basis.

 Most common example of this type of corrosion is the

rusting of iron and steel. Other examples are tarnishing
of aluminium, brass and silver, formation of green patina
on copper etc.

 It is a uniform type of corrosion.

Factors affecting atmospheric corrosion:

 Dust particles
Presence of dust particle enhance the rate of atmospheric
corrosion as they absorb moisture and various gases from
atmosphere.

 Gases in atmosphere
In industrial atmosphere gases like H2S and SO2 might be
present and they are harmful due to their conversion to H2SO4.

 Moisture content
Corrosion of metal like steel increases with increase in
humidity of atmosphere.

Remedies
1. Use of better alloy.
2. Use of various coatings.
 3. Reduction of humidity level.
4. Reduction of atmospheric pollution.

Intergranular Corrosion

 On a microscopic level, metals and there alloys have

small, distinguishable regions called grains. Within an
individual grain the orientation of the atomic arrangement
(called a lattice) is the same.

 Individual grains have different orientations and the

boundary between the grains is called the grain boundary.
Normally, grain boundaries are not very much reactive in
corrosion than the grain itself.

 Under certain conditions, however, the grain boundaries

are altered from the grain itself by impurities and/or
enrichment (or depletion) of one of the alloying elements.

 Heat treatment and welding can lead to changes metal

composition which may incite Intergranular corrosion. In
severe cases, Intergranular corrosion can lead to a marked
decrease in mechanical strength and can, in extreme cases,
turn the metal into a pile of individual grains. Which may
result in catastrophic failure.

 One of the most common examples of Intergranular

corrosion occurs in stainless steels. During welding of the
alloy, or heating in the temperature range of 550C to
850C.
 The alloy becomes sensitized or susceptible to
Intergranular corrosion as illustrated in Figure below. The
chromium carbide (Cr23C6) is not soluble in this
temperature range and precipitates out of the grain into the
grain boundary.

 As a result, the area of the grain adjacent to the grain

boundary is depleted of the chromium and becomes
anodic to the rest of the grain and to the grain boundary.
This phenomenon is known as sensitization of stainless
steel or weld decay.

Fig: Formation of chromium depleted region.

 The corrosion of this depleted grain boundary area is very

severe and occurs in environments and acids where the
alloy would not normally corrode.

 In practice sensitization of SS may occur due to one of the

three following reasons:
 Slow cooling of the alloy in the sensitization
temperature range during solidification or heat
treatment.
 During tempering after quenching.
  During welding of the alloy. During welding
operation the parent metal on both side of weld is
heated to sensitization range and this may result in
precipitation of Cr23C6 and cause Intergranular
corrosion. This is known as weld decay.

Fig: Weld decay phenomena

Remedies:

 The simplest solution to the stainless steel Intergranular

corrosion problem is to decrease the carbon contents
below 0.03%. This prevents the formation of the
chromium carbide and the chromium stays in solution.

 Rapid cooling in the sensitization temperature range.

 Addition of strong carbide former like Nb, W, V etc.

iii. Pitting corrosion

 Pitting is an extremely localized attack that eventually

results in holes in the metal.

 It is one of the most destructive forms of corrosion and

results in sudden failure.

 Basically, the alloys subject to pitting are those that rely

on an oxide film for protection, such as stainless steels.

 The initiation of a pit can be the result of the following:

a) Chemical attack, such as seawater on stainless steel.

b) Mechanical attack such as an impact or scratching that

removes small areas of the protective film.

c) Due to compositional inhomogeneity or surface defects.

Pitting in 18-8 SS by acid chloride solution

CHARACTERISTICS

Following are the characteristics of pitting corrosion:

1. Active metals are most susceptible to this type of attack,

e.g. chromium, aluminium and alloys containing these
elements.
2. Pits are usually formed randomly on the surface. They are
sometimes isolated or so close together that they look like
a rough surface.
3. Pits are, generally, described as a hole or cavity with the
surface diameter about the same or less than the depth.
4. It is often difficult to detect pits because of their small size
and because they are covered with corrosion products.
5. Pitting is a corrosion process which is autocatalytic, self-
stimulating and self-propagating.
6. Pits are usually elongated in the direction of gravity.
7. Pits are generally initiated on the upper surface of the
horizontally placed specimens.

8. Pitting usually occurs under stagnant conditions such as

crevices, liquid trapped in the part of an inactive pipe
system, or liquid stored in a container.
Mechanism

 Pitting nucleates by formation of a corrosion cell between

a small anodic area and large cathodic area. This small
anodic area is known as pit.
  This could be due to heterogeneity in metal, or in the film
on metal surface or presence of small areas of more plastic
strain.
Remedies
• Select suitable materials that show minimum proneness to
pitting in the type of environment being used.
• Control of environment aggressiveness through monitoring
chloride concentration level, acidity.
• Use of protective coatings.
• Application of cathodic protection.

iv. Corrosion Fatigue

 The simultaneous action of cyclic stress and chemical
attack is known corrosion fatigue.
 It can be defined as the reduction of fatigue strength due
to presence of corrosive environment.
 Corrosion fatigue can be defined as the reduction in
fatigue strength due to presence of corrosive environment.
 Previously formed pits act as notches and decreases the
fatigue strength. The rate of fatigue crack propagation
increases under corrosive environment.
 Fig: Fatigue curve(S-N) of ferrous material with and without corrosion

Prevention
 Lowering the tensile strength of the material.
 Reducing stress on the component.
 The choice of material for this type of service should be
based on its corrosion resistant properties rather than
fatigue properties.
 Nitriding, shot peening is done to avoid corrosion fatigue.
 Application of cathodic protection and inhibitor.

v. Galvanic Corrosion

 When two or more dissimilar metals/alloys immersed in a

corrosive solution(electrolyte) and externally brought in
electrical contact with each other, the existence of a
potential difference between them results in a flow of
current in the external circuit.
 Less corrosion resistant metal acts as anode suffering
degradation and the more resistant metal acts as cathode
with almost no degradation as compared to their behaviour
 in the same solution if they were not electrically connected
or would have been individually immersed in the solution.
 Driving force for the flow of current or corrosion is the
developed potential difference between the two metals.

Prevention
 Choose alloys which are close to each other in the
Galvanic series.
 Avoid area effect of a small anode and large cathode.
 Electrically insulate dissimilar metals wherever possible.
 Apply coatings with caution and arrange regular
maintenance particularly for the anodic portion.
 Using inhibitors to reduce the aggressiveness of the
environment.

vi. Stress corrosion cracking (SCC)

 The failure of material by combined action of a tensile

stress and corrosive medium is known as stress corrosion
cracking.

 It is believed that the corrosion causes a pit or surface

discontinuity to form on the metal which then functions to
act as a stress concentrator.

 The presence of a minimum threshold tensile stress,

coupled with the corrosion, causes the crack to propagate.
Additionally, during the initial corrosion, the tensile
stresses could cause the protective films on the surface to
 rupture, thereby exposing the metal to the corrosive
environment.

 In this type of corrosion, the tensile stress rupture the

passivated film which results easy corrosion of the
structure, which eventually results in initiation of crack.

 Stress-corrosion-cracking occurs with specific alloys

under certain conditions like: Specific corrosive
environment solution composition, minimum tensile
stress levels, temperature, and metal composition.

 Some examples of SCC are the brass and stainless steel

alloys. Specific brass alloys will crack in ammonia
containing environments when a minimum threshold
tensile stress is reached. Stainless steel alloys do not crack
in ammonia environments, but will crack in chloride
solutions.

Prevention

 Lowering the stress by annealing, or by using thicker

section, or by reducing the load.
 Modification or elimination of critical environment by
degasification or by adding inhibitors.
 Selection of proper alloy and by cathodic protection.
vii. Cavitation corrosion

 Cavitation is the deterioration of a surface caused by the

sudden formation and collapse of bubbles and voids due
to the turbulence in the liquid. It is generally marked by a
pitted or rough metal surface.

 Cavitation damage occurs on surfaces which are in contact

with fluids at high velocities and where frequent pressure
changes are encountered, e.g., hydraulic turbines, ship
propellers, etc.

 Cavitation damage can also occur in the absence of a

corrosive environment, but the attack becomes more
severe when there is combine action.
 Cavitation corrosion has been attributed to the combined
action of mechanical effect and corrosion.

 It is assumed that the collapsing vapour bubbles destroy

protective surface films increased corrosion. This
mechanism is shown schematically in Fig.

 The steps are as follows: (i) cavitation bubble forms on the

protective film; (ii) the bubbles collapse and destroy the
film; (iii) the newly exposed metal surface corrodes and
the film is reformed; (iv) Cavitation bubble forms at the
same spot; (V) the new bubble collapses and destroys the
film (vi) the exposed area corrodes and the film reforms.
Repetition of this process results in deep holes.
Prevention
 Proper selection of material.
 Use of cathodic protection.
 Application of coatings.
 By changing the design of structures.

viii. Fretting Corrosion

 It is a type of corrosion occurring at contact areas between

two surfaces under load subjected to vibration and slip.
 The basic requirements for this type of corrosion are: the
surface in contact must be under load, vibration or
repeated relative motion and plastic deformation.
 There are two mechanisms which have been proposed to
explain damage due to Fretting corrosion:

1. Wear Oxidation Mechanism: According to this

mechanism, the two surfaces make contact at only a small
number of high points, where cold welding or fusion
occurs due to applied load. These contact points are
ruptured during subsequent relative motion and as a result
fragments of metal are removed. These fragments
 immediately get oxidized due to their small size and
frictional heat (Fig. a). This process repeats itself.

2. Oxidation Wear Mechanism: According to this

mechanism, metal surfaces are protected from
atmospheric Oxidation by an adherent oxide film. When
metals are placed in contact under load and are
subsequently subjected to repeated motion, the oxide layer
ruptures at high points and results in oxide particles (Fig.
b). The exposed metal surface re-oxidizes, and the process
repeats itself.

Prevention
 Using hard-metals, or even cold-worked or shot-peened
metals reduce Fretting-corrosion.
 Use of gaskets to absorb vibrations and exclude oxygen at
surfaces.
 Increase the load on surfaces to prevent slip of surfaces.
 Lubricate the parts with low viscosity oils and grease.
ix. High temperature oxidation corrosion

 Corrosion of metal can occur in the absence of a liquid

electrolyte when it is exposed to an oxidizing gas, e.g.-,
oxygen, Sulphur, or halogens, at ambient or elevated
temperatures. This is sometimes called scaling, tarnishing,
dry corrosion, or high temperature oxidation.

 As the temperature increases, Oxidation resistance of most

metals decreases. This type of attack is a serious problem
in many major industries, such as an aircraft, automobile,
chemical, electrical, metallurgical, paper and pulp, and
power.

 In one of the earliest studies on oxidations, Piling and

Bedworth proposed that the oxidation resistance is related
to the volume ratio of oxide and metal. This ratio is called
Pilling-Bed- worth ratio.

 The ratio R indicates the volume of oxide formed from a

unit volume of metal. If the value of R is close to unity (1)
then the oxide layer is supposed to be a protective layer.

Prevention
 The loss due to high temperature oxidation can be
minimized by using High temperature alloys like Ni-
alloys, use of coatings.
x. Stray Current Corrosion

 Corrosion can be accelerated by the action of electrical

currents entering a metal from some external source such
as a generator or a battery and leaving the metal to
continue its flow in whole or part.
 Stray current corrosion refers to type of corrosion
resulting from stray current- the current flowing through
paths other than the intended circuit.

 All metallic structures buried underground are susceptible

to this type of corrosion. Ex: DC railways, tunnels,
underground pipe lines etc.

 This corrosion is independent of the environmental

factors.

Prevention
 Identification of the stray current source.
 Maintaining good electrical connection and insulation.
 Installation of impressed current cathodic protection.
 Chapter - 6
Corrosion Prevention

Corrosion occurs when metals come in contact with a corrosive

atmosphere. Thus, corrosion can be prevented by:

1. Change of metal/alloy
2. Design improvement
3. Change of metal electrode potential
4. Use of coating
5. Change of environment

Cathodic Protection
 It is a method of reducing or preventing corrosion of a
metal by making it cathode in the electrolytic cell. There
are two methods available for cathodic protection:

I. Sacrificial anode method

II. Impressed current method

I. Sacrificial anode method

 In this method, another metal, which has more negative
electrode potential than the structure to be protected, is
connected electrically to the structure, which now acts like
a cathode.
 The structure is protected at the sacrifice (corrosion) of
another metal, and that is why, this name is given to the
method.
 Mg and Mg alloy are widely used. Zn is also often used.
Sacrificial anodes are replaced as soon as consumed.

 This method is used for protection of under-water parts of

ships, underground pipes, steel water-tanks, water heaters,
condenser-tubes, oil-cargo-ballast tanks etc. Galvanised
sheet is basically sacrificial-protection of steel, where Zn
is sacrificed.

II. Impressed current method

 In this method, the given metallic structure is made

cathode by the use of external current by connecting the
negative terminal of the external power-supply source to
the metallic structure, and the positive is connected to an
inert anode of scrap steel, aluminium, graphite, or silicon-
iron.

 Apart from pipe-lines, underground cables of aluminium,

lead; storage tanks, heat-exchangers, steel-gates exposed
to sea-water, hulls of ships are protected by this method.
  Often stray-current effects are encountered in this type of
cathodic protection.

Anodic Protection

 It is a technique to control the corrosion of a metal

surface by making it anode of an electrochemical cell by
controlling the electrode potential in a zone where the
metal is passive.

 This technique is only applicable to those metals which

exhibit passivation (protective film).

 This technique is mostly used for steel and stainless steel

in extreme corrosive conditions.
Coatings

 Cost is a very important factor while choosing an

engineering material. Instead of using a costly non-
corroding material an easily corrodible alloy like steel can
be used by protecting it from environment.

 By far the most important protective mean is one kind of

thin coating. The chief function of such a coating is to
provide an effective barrier between the metal and its
environment.

 The coat itself should have good resistance to corrosion,

should be adherent and cover the metal completely. The
coatings are broadly classified as
I. Metallic Coatings
II. Non-metallic coatings

I. METALLIC COATINGS

 Protecting the metals by metal-coating is an old and very

widely used practice as they are more durable, more
decorative and provide better protection against corrosion.

Metallic coatings are classified as:

i. Cathodic Coatings
 In such a type of coating, the coating metal is cathodic
with respect to the base metal.

 Coatings of tin, nickel and chromium on steel are cathodic

coatings as these are higher than steel in the galvanic
series.
  These coatings provide a physical barrier between the
metal and the environment. When the coating is dense,
non-porous, continuous corrosive medium did not come in
contact with base metal, and the base metal does not
corrode.

 Coating being cathodic does not corrode. Ex- Nickel and

chromium plating on steel for automobile, coating on tin
plate tube used as food container.

ii. Anodic Coatings

 The coating metal is anodic as compared to the underlying

metal. The anodic coating provide galvanic protection to
the base metal, in addition to acting as a physical barrier
between the base metal and the environment. This type of
coatings offers a sacrificial type cathodic protection.
Ex: Galvanised corrugated steel sheets used for roofing,
automobile parts etc.

II. NON-METALLIC COATINGS

These coatings can further be divided into two types

(i) Organic coatings (ii) Inorganic coatings

(i) Organic coatings

These are the inert organic barriers applied on materials as a

barrier to corrosion.
Ex: Paints, varnishes, enamel etc.
These types of coatings required surface preparation, primary
coating (primer) before application of organic coating.

(ii) Inorganic Coatings

Various inorganic coatings on metal surface are:

Vitreous coating or glass-steel- Steels with glass coatings,
where glass linings act as the barrier.
Portland cement – It also known as concrete which saves the
TMT bars getting corroded.
Chemical conversion coating – These are some chemicals
which on application on the metal surface, reacts with the metal
and creates a passivated layer.

INHIBITORS
 These are the substances which when added to the
corrosive environment decreases the rate of corrosion by
reducing the severity of the environment.

 Inhibitors either act as a barrier by forming an adsorbed

layer or retard the cathodic or anodic reaction.

Types of Inhibitors
1. Chemical Passivators: Certain substances while added to
the corrosive medium results in formation of passivated layer
on the metal surface.
Ex: Chromate, Nitrate and ferritic salts.

2. Absorption Inhibitors: These are organic compounds

which get absorbed on the entire anodic as well as cathodic
surfaces to act as a blanket and thus affect the reactions.
Inhibitors doesn’t allow the acids to react with base metal.
Ex: Hexamethylene tetramine and thiourea etc.
3. Film-Forming Inhibitors: These are the inhibitors which
stop corrosion by forming a blocking or barrier film of a
material other than the actual inhibiting species.
Ex: Calcium salt, zinc salt, benzoate etc.

4. Vapour-phase Inhibitors: When these types of inhibitors

are added a vapour, phase is created. This vapour gets
condensed onto the metal surface and it is spread throughout.
The condensed phase is hydrophobic (water repellent) so saves
the metal from getting corroded.

Ex: Dicyclohexylamine, benzotiazole etc.